三（三甲代甲硅烷基）亚磷酸盐

反应条件: temp:0.00; pressure:0.00; stir:

反应条件: temp:0.00; pressure:0.00; stir:

反应条件: temp:80.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: To a stirred suspension of 5-amino-2-(4-methoxy-2-methylphenethyl)benzo[f][1,7]naphthyridine-8-carbaldehyde (2-2) (Example 9—Step 1) (1.0 equiv.) in toluene (0.27 M) was added tris(trimethylsilyl) phosphite (1.0 equiv.). The reaction was stirred at 80° C. for 60 minutes, then solvents were removed, and the resulting residue was taken up in DMSO (0.27 M), and IBX (1.5 equiv.) was added. The reaction was stirred at room temperature for 2.5 hour, and was filtered and directly purified on RP-HPLC using a C18 column, eluting with 10-40% 95:5 (MeCN/5 mM NH4OAc) in 10 mM NH4OAc (pH 9) gradient. The fractions containing the product were combined and concentrated in vacuo to give 5-amino-2-(4-methoxy-2-methylphenethyl)benzo[f][1,7]naphthyridine-8-carbonylphosphonic acid (14) as a solid. 1H NMR (Dimethylsulfoxide-d6): δ 9.84 (s, 1H), 9.35 (s, 1H), 9.09 (s, 1 H), 8.89 (s, 1 H), 8.76 (d, 1H, J=8.4 Hz), 8.60 (s, 1H), 8.19 (d, 1H, J=8.8 Hz), 7.04 (d, J=8.8 Hz, 1H), 6.70 (d, 1H, J=2.8 Hz), 6.62 (dd, 1H, J=2.8, 8.4 Hz), 3.64 (s, 3H), 3.15-3.09 (m, 2H), 2.97-2.91 (m, 2H), 2.23 (s, 3H). LRMS [M+H]=452.1 solvents were removed IBX (1.5 equiv.) was added The reaction was stirred at room temperature for 2.5 hour was filtered directly purified on RP-HPLC eluting with 10-40% 95:5 (MeCN/5 mM NH4OAc) in 10 mM NH4OAc (pH 9) gradient The fractions containing the product concentrated in vacuo

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: Tris(trimethylsilyl) phosphite (2 molar equiv.) in an appropriate dry solvent was added dropwise to a stirred solution of acetyl chloride (1 molar equiv.) in an appropriate dry solvent at room temperature and the mixture stirred for 10 minutes. Excess methanol was then added and the mixture stirred for 5 minutes to decompose the silyl esters. The volatile components in the reaction mixture were then removed under reduced pressure to leave the title compound in good purity. the mixture stirred for 5 minutes The volatile components in the reaction mixture were then removed under reduced pressure

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: Triethylamine (40.4 g, 40.4 mmol) was added dropwise to a mechanically stirred solution of phosphorous acid (16.5 g, 201 mmol) and chlorotrimethylsilane (44 g, 405 mmol) in diethyl ether (1200 cm3). Immediately, a white precipitate of triethlyamine hydrochloride formed. After the addition was complete (2 h) the mixture was stirred for a further 2 hours. The insoluble salt was removed by filtration and the filtrate concentrated to about 200 cm3. The small quantity of additional precipitate formed during this process was subsequently filtered off and the filtrate evaporated to give a cloudy liquid. The product was purified by distillation under reduced pressure, the fraction boiling in the range 45-50° C. at 0.1 mbar being collected. The bis(trimethylsilyl) phosphite was isolated as a colourless oil (35 g, 77%). 31P NMR: δ−12.8. Chlorotrimethylsilane (20 g, 185 mmol) was added dropwise to a stirred solution of bis(trimethylsilyl)phosphite (30 g, 132 mmol) and N,N-diethyltrimethylsilylamine (20 g, 137 mmol) and the mixture stirred at room temperature for 1 h. The solid formed was removed by filtration and the filtrate distilled in vacuo. A colourless fraction boiling at 77-80° C. at 0.1 mbar was collected (30 g, 75%). 31P NMR: δ+116.3. The solid formed was removed by filtration the filtrate distilled in vacuo A colourless fraction boiling at 77-80° C. at 0.1 mbar was collected (30 g, 75%)

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: A solution of 4.3 g (14 mmol) of 4-(phenylsulfonyl)benzyl bromide and 30 g (0.1 mole) of tris-trimethylsilylphosphite was heated at 120° C. for 18 hours. The excess tris-trimethylsilylphosphite was distilled off under reduced pressure. The residue was dissolved in 200 ml of 9:1 tetrahydrofuran/water and was allowed to stand at room temperature for 18 hours. The tetrahydrofuran was evaporated and the resulting solids were filtered and washed with water to give 1.4 g of product; m.p. 217-219° C. The excess tris-trimethylsilylphosphite was distilled off under reduced pressure The residue was dissolved in 200 ml of 9:1 tetrahydrofuran/water The tetrahydrofuran was evaporated the resulting solids were filtered washed with water

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: 2-Fluoro-5-nitrobenzaldehyde (1.75 g, 10.0 mmol) was dissolved in tetrahydrofuran(50 mL). Tris(trimethylsilyl)phosphite (3.45 mL, 10.0 mmol) was added. The reaction mixture was stirred for 2.5 hours. Evaporation gave an oil which was dissolved in ethanol-ether. Addition of cyclohexylamine (1.14 mL,10.0 mmol) gave a solid salt which was filtered. Recrystallization from water gave 1.88 g (53.0%) of analytically pure product, mp 226-231° C.1H NMR (DMSO): d, 8.47 (m,1H), 8.11 (m,1H), 7.34 (t,1H), 4.85 (d,1H). MS (neg FAB): 249.9 (M-H). C7H7FNO6P/C6H13N. Evaporation gave an oil which gave a solid salt which was filtered Recrystallization from water gave 1.88 g (53.0%) of analytically pure product, mp 226-231° C